Cross-section through the frontal Japan Trench subduction zone: Geochemical evidence for fluid flow and fluid–rock interaction from DSDP and ODP pore waters and sediments

Abstract Fluids and sediments from Deep Sea Drilling Project/Ocean Drilling Program Legs (56, 57, 87 and 186) along a transect extending from the subducting plate, across the midslope and upper slope of the Japan Trench forearc were analyzed for B and B isotopes in order to assess their composition and fluid–sediment interaction. At the reference Site 436 on the subducting plate, changes in B contents and B isotopes are controlled by the lithology and diagenesis only. The midslope Sites 440 and 584 showed stronger variations in the B geochemistry, which can be related to diagenesis and tectonic dewatering along faults. The strongest changes in the B geochemistry were observed on the upper slope Sites 1150 and 1151, where profound down‐hole freshening (chlorinities as low as ～310 mmol) coincides with a B enrichment (up to 9.3 × seawater concentration). The B isotope pore fluid profile of Site 1150 displayed a bimodal variation with depth, first increasing to values more positive than seawater, then shifting to lower signatures typical for deep‐seated fluids, whereas Site 1151 showed a constant B decrease with depth. Sites 1150 and 1151 sediments showed B increases with depth to values as high as ～164 p.p.m. and isotopic compositions ranging from ～+4 to ?9‰. A linear decrease in B_solid/B_fluid ratio, suggests that B geochemistry of the upper slope sites is controlled by fluid–rock interaction and deep‐seated fluid flow, whereas constant B_solid/B_fluid ratios were observed at the reference site on the incoming plate. This fluid overprint is probably caused by normal faults in the sediment cover which might be interconnected to deep thrusts in the underlying Cretaceous accreted wedge. This suggests that the erosive Japan Trench margin is characterized by back‐flux of deep‐seated, B‐enriched fluids into the ocean, which is facilitated by extensional normal faulting as a result of tectonic erosion and subsidence.     

Subduction erosion of forearc mantle wedge implicated in the genesis of the South Sandwich Island (SSI) arc: Evidence from boron isotope systematics

The South Sandwich volcanic arc is sited on a young oceanic crust, erupts low-K tholeiitic rocks, is characterized by unexotic pelagic and volcanogenic sediments on the down-going slab, and simple tectonic setting, and is ideal for assessing element transport through subduction zones. As a means of quantifying processes attending transfer of subduction-related fluids from the slab to the mantle wedge, boron concentrations and isotopic compositions were determined for representative lavas from along the arc. The samples show variable fluid-mobile/fluid-immobile element ratios and high enrichments of B/Nb (2.7 to 55) and B/Zr (0.12 to 0.57), similar to those observed in western Pacific arcs. δ¹¹B values are among the highest so far reported for mantle-derived lavas; these are highest in the central part of the arc (+ 15 to + 18‰) and decrease toward the southern and northern ends (+ 12 to + 14‰). δ¹¹B is roughly positively correlated with B concentrations and with ⁸⁷Sr/⁸⁶Sr ratios, but poorly coupled with other fluid-mobile elements such as Rb, Ba, Sr and U. Peridotites dredged from the forearc trench also have high δ¹¹B (ca. + 10‰) and elevated B contents (38–140 ppm). Incoming pelagic sediments sampled at ODP Site 701 display a wide range in δ¹¹B (+ 5 to ? 13‰; average = ? 4.1‰), with negative values most common. The unusually high δ¹¹B values inferred for the South Sandwich mantle wedge cannot easily be attributed to direct incorporation of subducting slab materials or fluids derived directly therefrom. Rather, the heavy B isotopic signature of the magma sources is more plausibly explained by ingress of fluids derived from subduction erosion of altered frontal arc mantle wedge materials similar to those in the Marianas forearc. We propose that multi-stage recycling of high-δ¹¹B and high-B serpentinite (possibly embellished by arc crust and volcaniclastic sediments) can produce extremely ¹¹B-rich fluids at slab depths beneath the volcanic arc. Infiltration of such fluids into the mantle wedge likely accounts for the unusual magma sources inferred for this arc.     

A Geochemical Approach to Determine Sources and Movement of Saline Groundwater in a Coastal Aquifer

Geochemical evaluation of the sources and movement of saline groundwater in coastal aquifers can aid in the initial mapping of the subsurface when geological information is unavailable. Chloride concentrations of groundwater in a coastal aquifer near San Diego, California, range from about 57 to 39,400 mg/L. On the basis of relative proportions of major‐ions, the chemical composition is classified as Na‐Ca‐Cl‐SO₄, Na‐Cl, or Na‐Ca‐Cl type water. δ²H and δ¹⁸O values range from ?47.7‰ to ?12.8‰ and from ?7.0‰ to ?1.2‰, respectively. The isotopically depleted groundwater occurs in the deeper part of the coastal aquifer, and the isotopically enriched groundwater occurs in zones of sea water intrusion. ⁸⁷Sr/⁸⁶Sr ratios range from about 0.7050 to 0.7090, and differ between shallower and deeper flow paths in the coastal aquifer. ³H and ¹⁴C analyses indicate that most of the groundwater was recharged many thousands of years ago. The analysis of multiple chemical and isotopic tracers indicates that the sources and movement of saline groundwater in the San Diego coastal aquifer are dominated by: (1) recharge of local precipitation in relatively shallow parts of the flow system; (2) regional flow of recharge of higher‐elevation precipitation along deep flow paths that freshen a previously saline aquifer; and (3) intrusion of sea water that entered the aquifer primarily during premodern times. Two northwest‐to‐southeast trending sections show the spatial distribution of the different geochemical groups and suggest the subsurface in the coastal aquifer can be separated into two predominant hydrostratigraphic layers.     

Gypsum and halite from the Mid-Atlantic Ridge,DSDP Site 395

Gypsum and halite crystals, together with saponite and phillipsite, were found in a vein in a basalt sill 625 m below the sea floor at DSDP Site 395A, located 190 km west of the crest of the Mid-Atlantic Ridge. The δ³⁴S value of the gypsum (+19.4‰) indicates a seawater source for the sulfate. The δ¹⁸O values of the saponite (+19.9‰) and phillipsite (+18.1‰) indicate either formation from normal seawater at about 55°C or formation from¹⁸O-depleted seawater at a lower temperature.The gypsum (which could be secondary after anhydrite) was formed by reaction between Ca²⁺ released from basalt and SO₄^2? in circulating seawater. The halite could have formed when water was consumed by hydration of basalt under conditions of extremely restricted circulation. A more probable mechanism is that the gypsum was originally precipitated as anhydrite at temperatures above 60°C. As the temperature dropped the anhydrite converted to gypsum. The conversion would consume water, which could cause halite precipitation, and would cause an increase in the volume of solids, which would plug the vein and prevent subsequent dissolution of the halite.     

Constraints on the state of in situ effective stress and the mechanical behavior of ODP Leg 186 claystones in the Japan Trench forearc

Abstract The Japan Trench forearc offshore Honshu Island in northeast Japan, where the 130‐m.y.‐old Pacific oceanic plate is presently subducted, was drilled during the Ocean Drilling Program Leg 186. Results from mechanical and sedimentological studies of claystones recovered from Sites 1150 and 1151 in the overlying erosional forearc wedge are reported in the present study. Although many physical properties are similar in the seismic (Site 1150) and aseismic portion (Site 1151) of the shallow forearc, Site 1150 displayed a higher abundance of open fractures, two prominent fault zones and enigmatic pore fluid signatures in the claystones. The abundance of weak mineral phases, together with high smectite contents (from X‐ray diffraction), control the low friction coefficients of 0.33–0.39 of the claystones in ring‐shear experiments. Results from triaxial testing proposed overall low magnitudes of in situ effective vertical stress, with somewhat lower values at Site 1150 than at Site 1151. Similarly, samples from Site 1150 displayed slightly higher pore fluid pressures than those at Site 1151. The high sediment porosities, which are in part also a result of intact diatom tests (from scanning electron microscope), together with the anomalous fluid signatures and elevated pore fluid pressures, could very likely result from upward migration and influx of deep‐seated waters. Dewatering reactions at depth result in enhanced pore fluid pressure transients along out‐of‐sequence thrusts and consequently lower effective stress. At depths greater than that of Leg 186 drilling, elevated pressure–temperature conditions trigger mineral transformation and cementation, which result in increasing friction, unstable sliding and seismic rupture. Such earthquakes could have repeatedly disaggregated the consolidated claystone fabrics at the seismic site, and could be responsible for differences in yield strength and cementation when compared to the aseismic Site 1151.     

Environmental isotopic and hydrochemical characteristics of groundwater systems in Daying and Qicun geothermal fields,Xinzhou Basin,Shanxi, China

The conceptual hydrogeological model of the low to medium temperature Daying and Qicun geothermal fields has been proposed, based on hydrochemical characteristics and isotopic compositions. The two geothermal fields are located in the Xinzhou basin of Shanxi, China and exhibit similarities in their broad‐scale flow patterns. Geothermal water is derived from the regional groundwater flow system of the basin and is characterized by Cl·SO₄‐Na type. Thermal water is hydrochemically distinct from cold groundwater having higher total dissolved solids (TDS) (>0·8 g/l) and Sr contents, but relatively low Ca, Mg and HCO₃ contents. Most shallow groundwater belongs to local flow systems which are subject to evaporation and mixing with irrigation returns. The groundwater residence times estimated by tritium and ¹⁴C activities indicate that deep non‐thermal groundwater (130–160 m) in the Daying region range from modern (post‐1950s) in the piedmont area to more than 9·4 ka BP (Before Present) in the downriver area and imply that this water belong to an intermediate flow system. Thermal water in the two geothermal fields contains no detectable active ¹⁴C, indicating long residence times (>50 ka), consistent with this water being part of a large regional flow system. The mean recharge elevation estimated by using the obtained relationship Altitude (m) = ? 23·8 × δ²H (‰ ) ? 121·3, is 1980 and 1880 m for the Daying and Qicun geothermal fields, respectively. The annual infiltration rates in the Daying and Qicun geothermal fields can be estimated to be 9029 × 10³ and 4107 × 10³ m³/a, respectively. The variable ⁸⁶Sr/⁸⁷Sr values in the thermal and non‐thermal groundwater in the two fields reflect different lithologies encountered along the flow path(s) and possibly different extents of water‐rock interaction. Based on the analysis of groundwater flow systems in the two geothermal fields, hydrogeochemical inverse modelling was performed to indicate the possible water‐rock interaction processes that occur under different scenarios. Copyright © 2010 John Wiley & Sons, Ltd.     

Strontium and oxygen isotopic composition of some basalts from Hole 504B,Costa Rica Rift,DSDP Legs 69 and 70

Seventeen whole-rock samples, generally taken at 25–50 m intervals from 5 to 560 m sub-basement in Hole 504B, drilled in 6.2 m.y. old crust, were analysed for⁸⁷Sr/⁸⁶Sr ratios, Sr and Rb concentrations, and¹⁸O/¹⁶O ratios. Sr isotope ratios for 8 samples from the upper 260 m of the hole range from 0.70287 to 0.70377, with a mean of 0.70320. In the 330–560 m interval, 5 samples have a restricted range of 0.70255–0.70279, with a mean of 0.70266, the average value for fresh mid-ocean ridge basalts (MORB). In the 260–330 m interval, approximately intermediate Sr isotopic ratios are found.δ¹⁸O values (‰) range from 6.4 to 7.8 in the upper 260 m, 6.2–6.4 in the 270–320 m interval, and 5.8–6.2 in the 320–560 m interval. The values in the upper 260 m are typical for basalts which have undergone low-temperature seawater alteration, whereas the values for the 320–560 m interval correspond to MORB which have experienced essentially no oxygen isotopic alteration.The higher⁸⁷Sr/⁸⁶Sr and¹⁸O/¹⁶O ratios in the upper part of the hole can be interpreted as the result of a greater overall water/rock ratio in the upper part of the Hole 504B crust than in the lower part. Interaction of basalt with seawater(⁸⁷Sr/⁸⁶Sr=0.7091) increased basalt⁸⁷Sr/⁸⁶Sr ratios and produced smectitic alteration products which raised whole-rock δ¹⁸O values. Seawater circulation in the lower basalts may have been partly restricted by the greater number of relatively impermeable massive lava flows below about 230 m sub-basement. These flows may have helped to seal off lower basalts from through-flowing seawater.     

Origin and Evolution of Aquitard Porewater in the Western Coastal Plain of Bohai Bay,China

High‐salinity paleowater from low‐permeability aquitards in coastal areas can be a major threat to groundwater resources; however, such water has rarely been studied. The chemical and isotopic compositions of porewater extracted from a 200‐m‐thick Quaternary sedimentary sequence in the western coastal plain of Bohai Bay, China, were analyzed to investigate the salinity origin and chemical evolution of porewater in aquitards. Porewater samples derived at depths shallower than 32 m are characterized by Cl‐Na type saline water (total dissolved solids [TDS], 10.9–84.3 g/L), whereas those at depths greater than 32 m comprise Cl·SO₄‐Na type brackish water (TDS, 2.2–6.3 g/L). Saline porewater is interpreted as evaporated seawater prior to halite saturation, as evidenced by Cl‐Br relationships. Although substantial dilution of saline porewater with meteoric water is supported by a wider Cl^? range and δ²H‐δ¹⁸O covariance, the original marine waters were not completely flushed out. The deeper brackish porewater is determined to be a mixture of fresher porewater and brine groundwater and had a component of old brine of less than 10%, as indicated by a mixing model defined using δ²H and Cl^? tracers. Porewater δ²H‐δ¹⁸O relationships and negative deuterium excess ranging from ?25.9‰ to ?2.9‰ indicate the existence of an arid climate since Late Pleistocene in Tianjin Plain. The aquitard porewaters were chemically modified through water‐rock interactions due to the long residence time.     

Spatial and temporal perspectives on spring break‐up flooding in the Slave River Delta,NWT

Spatial and temporal patterns of spring break‐up flooding in the Slave River Delta (SRD), Northwest Territories, are characterized during three years (2003–2005) using water isotope tracers and total inorganic suspended sediment (TSS) concentrations measured from lakewater samples collected shortly after the spring melt. Strongly contrasting spring melt periods led to a moderate flood in 2003, no flooding in 2004 and widespread flooding in 2005. Flooded lakes have isotopically‐depleted δ¹⁸O (δ²H) signatures, ranging between ? 19·2‰ (?145‰) and ? 17·1‰ (?146‰) and most have high TSS concentrations (>10 mg L^?1), while non‐flooded lakes have more isotopically‐enriched δ¹⁸O (δ²H) signatures, ranging between ? 18·2‰ (?149‰) and ? 10·6‰ (?118‰) and low TSS concentrations (<10 mg L^?1). These results, in conjunction with the isotopic signatures of Slave River water and snowmelt, are used to estimate the proportion of river‐ or snowmelt‐induced dilution in delta lakes during the spring of each study year. Calculations indicate river flooding caused dilution of ～70–100% in delta lakes, while snowmelt dilution in the absence of river flooding ranged from ～0–56%. A positive relationship exists between the spatial extent of spring flooding in the SRD and level and discharge on the Slave River and upstream tributaries, suggesting that upstream flow generation plays a key role in determining the magnitude of spring flooding in the SRD. Parallel variations in the 46‐year instrumental Slave River discharge record and flood stratigraphy in the active delta indicate that there is potential for extending the flood history of the SRD, a development that will contribute to a more robust understanding of the drivers of historic, contemporary and future flood frequency in the delta. Copyright © 2008 John Wiley & Sons, Ltd.     

Carbon isotope stratigraphy of Torinosu‐type limestone in the western Paleo‐Pacific and its implication to paleoceanography in the Late Jurassic and earliest Cretaceous

Carbon isotope stratigraphy of the Late Jurassic and earliest Cretaceous was revealed from Torinosu‐type limestone, which was deposited in a shallow‐marine setting in the western Paleo‐Pacific, in Japan. Two sections were examined; the Nakanosawa section of the late Kimmeridgian to early Tithonian age (Fukushima Prefecture, Northeast Japan), and the Furuichi section of the late Kimmeridgian to early Berriasian age (Ehime Prefecture, Southwest Japan). The age‐model was established using Sr isotope ratio and fossil occurrence. The limestone samples have a low Mn/Sr ratio (mostly <0.5) and lack a distinct correlation between δ¹³C and δ¹⁸O, indicating a low degree of diagenetic alteration. Our composite δ¹³C profile from the two limestone sections shows three stratigraphic correlation points that can be correlated with the profiles of relevant ages from the Alpine Tethyan region: a large‐amplitude fluctuation (the lower upper Kimmeridgian, ～152 Ma), a positive anomaly (above the Kimmeridgian/Tithonian boundary, ～150 Ma), and a negative anomaly (the upper lower Tithonian, ～148 Ma). In addition, we found that δ¹³C values of the Torinosu‐type limestone are ～1‰ lower than the Tethyan values in the late Kimmeridgian. This inter‐regional difference in δ¹³C values is likely to have resulted from a higher productivity and/or an organic burial in the Tethyan region. The difference gradually reduces and disappears in the late Tithonian, where the Tethyan and our δ¹³C records show similar stable values of 1.5–2.0‰. This isotopic homogenization is probably due to changes in the continental distribution and the global ocean circulation, which propagated the ¹³C‐depleted signature from the larger Paleo‐Pacific to the smaller Tethys Ocean during this time.     

Lithium isotope variations in Tonga–Kermadec arc–Lau back‐arc lavas and Deep Sea Drilling Project (DSDP) Site 204 sediments

Lithium isotopes have been identified as a promising tracer of subducted materials in arc lavas due to the observable variations in related reservoirs such as subducting sediments and altered oceanic crust. The Tonga–Kermadec arc–Lau back‐arc provides an end‐member of subduction zones with the coldest thermal structure on Earth. Reported here are Li isotope data for 14 lavas from the arc front and 7 back‐arc lavas as well as 12 pelagic and volcaniclastic sediments along a profile through the sedimentary sequence at DSDP Site 204. The arc and back‐arc lavas range from basalts to dacites in composition with SiO₂ = 48.3–65.3 wt% over which Li concentrations increase from 2 ppm to 16 ppm. Li/Y ratios range from 0.08 to 0.77 and from 0.24 to 0.65 in the arc and back‐arc lavas, respectively. The majority of the lavas have δ⁷Li that ranges from 2.5 ‰ to 5.0 ‰ with an average of (3.6 ±0.7) ‰, similar to that reported from other arcs and there is no distinction between the arc front and back‐arc lavas. The pelagic sediments have variable Li concentrations (33–133 ppm) and δ⁷Li that ranges from 1.2 ‰ to 10.2 ‰ while the volcaniclastic sediments have an even greater range of Li concentrations (3.6–165 ppm) and generally higher δ⁷Li values (8–14 ‰). However, δ⁷Li in the lavas does not correlate with commonly used trace element ratio or isotope signatures indicative of slab‐derived fluids or the sediments. This is probably because the range of δ⁷Li in the lavas and sediments overlap. Calculated sediment mass‐balance models require significantly more sediment than previous estimates based on Th–Nd–Be isotopes. This may indicate that a sizeable proportion of the total Li budget in the lavas is provided by Li‐enriched fluids from the subducting sediments and/or altered oceanic crust.     

The strontium isotopic composition of seawater,and seawater-oceanic crust interaction

The⁸⁷Sr/⁸⁶Sr ratio of seawater strontium (0.7091) is less than the⁸⁷Sr/⁸⁶Sr ratio of dissolved strontium delivered to the oceans by continental run-off (～0.716). Isotope exchange with strontium isotopically lighter oceanic crust during hydrothermal convection within spreading oceanic ridges can explain this observation. In quantitative terms, the current⁸⁷Sr/⁸⁶Sr ratio of seawater (0.7091) may be maintained by balancing the continental run-off flux of strontium (0.59 × 10¹² g/yr) against a hydrothermal recirculation flux of 3.6 × 10¹² g/yr, during which the⁸⁷Sr/⁸⁶Sr ratio of seawater drops by 0.0011. A concomitant mean increase in the⁸⁷Sr/⁸⁶Sr ratio of the upper 4.5 km of oceanic crust of 0.0010 (0.7029–0.7039) should be produced. This required⁸⁷Sr enrichment has been observed in hydrothermally metamorphosed ophiolitic rocks from the Troodos Massif, Cyprus.The post-Upper Cretaceous increase in the strontium isotopic composition of seawater(～0.7075–0.7091) covaries smoothly with inferred increase in land area. This suggests that during this period the main factor which has caused variability in the⁸⁷Sr/⁸⁶Sr ratio of seawater strontium could have been variation in the magnitude of the continental run-off flux caused by variation in land area. Variations in land area may themselves have been partly a consequence of variations in global mean sea-floor spreading rate.     

Linkage of deep sea rapid acidification process and extinction of benthic foraminifera in the deep sea at the Paleocene/Eocene transition

Ocean Drilling Program Leg 199 Site 1220 provides a continuous sedimentary section across the Paleocene/Eocene (P/E) transition in the carbonate‐bearing sediments on 56–57 Ma oceanic crust. The large negative δ¹³C shift in seawater is likely due to the disintegration of methane hydrate, which is expected to be rapidly changed to carbon dioxide in the atmosphere and well‐oxygenated seawater, leading to a reduction in deep‐sea pH. A pH decrease was very likely responsible for the emergence of agglutinated foraminiferal fauna as calcareous fauna was eliminated by acidification at the P/E transition at Site 1220. The absence of the more resistant calcareous benthic foraminifera and the presence of the planktonic foraminifera at Site 1220 is interesting and unique, which indicates that calcareous benthic foraminifera suffered greatly from living on the seafloor. Box model calculation demonstrates that, assuming the same mean alkalinity as today, pCO₂ must increase from 280 ppm to about 410 ppm for the calcite undersaturation in the deep ocean and for the oversaturation in the surface ocean during the P/E transition. The calculated increased pCO₂ coincides with paleo‐botanical evidence. The current global emission rate (～7.3 peta (10¹⁵) gC/y) of anthropogenic carbon input is approximately 30 times of the estimate at the P/E transition. The results at the P/E transition give an implication that the deep sea benthic fauna will be threatened in future in combination with ocean acidification, increased sea surface temperature and more stratified surface water.     

The hydrothermal system of Mendeleev Volcano,Kunashir Island,Kuril Islands: The geochemistry and the transport of magmatic components

This paper reports a detailed geochemical study of thermal occurrences as observed in the edifice and on the flanks of Mendeleev Volcano, Kunashir Island in August and September 2015. We showed that three main types of thermal water are discharged there (neutral chloride sodium, acid chloride sulfate, and acid sulfate types); these waters exhibit a zonality that is typical of volcano-hydrothermal island arc systems. Spontaneous and solfataric gases have relatively low ³He/⁴He ratios, ranging between 5.4Ra and 5.6Ra, and δ¹³C-CO₂ between –4.8‰ and –3.1‰, and contain a light isotope of carbon in methane (δ¹³C ≈ –40‰). Gas and isotope geothermometers yield relatively low temperatures around 200°C. The isotope compositions in all types of water are similar to that of local meteoric water. The distribution of microcomponents varies among different types. The isotope composition of dissolved Sr varies considerably, from 0.7034 as observed in Kunashir rocks on an average to 0.7052 in coastal springs, which may have resulted from admixtures of seawater. The total hydrothermal transport rates of magmatic Cl and SO₄, as observed for Mendeleev Volcano, are 7.8 t/d and 11.6 t/d, respectively. The natural outward transport of heat by the volcano’s hydrothermal system is estimated as 21 MW.     

Hydrothermal alteration and tectonic evolution of an intermediate- to fast-spreading back-arc oceanic crust: Late Ordovician Solund-Stavfjord ophiolite, western Norway

Abstract The Solund‐Stavfjord ophiolite complex (SSOC) in western Norway represents a remnant of the Late Ordovician oceanic lithosphere, which developed in an intermediate‐ to fast‐spreading Caledonian back‐arc basin. The internal architecture and magmatic features of its crustal component suggest that the SSOC has a complex, multistage sea floor spreading history in a supra‐subduction zone environment. The youngest crustal section associated with the propagating rift tectonics consists of a relatively complete ophiolite pseudostratigraphy, including basaltic volcanic rocks, a transition zone between the sheeted dyke complex and the extrusive sequence, sheeted dykes, and high‐level isotropic gabbros. Large‐scale variations in major and trace element distributions indicate significant remobilization far beyond that which would result from magmatic processes, as a result of the hydrothermal alteration of crustal rocks. Whereas K₂O is strongly enriched in volcanic rocks of the extrusive sequence, Cu and Zn show the largest enrichment in the dyke complex near the dyke–volcanic transition zone or within this transition zone. The δ¹⁸O values of the whole‐rock samples show a general depletion structurally downwards in the ophiolite, with the largest and smallest variations observed in volcanic rocks and the transition zone, respectively. δ¹⁸O values of epidote–quartz mineral pairs indicate 260–290°C for volcanic rocks, 420°C for the transition zone, 280–345°C for the sheeted dyke complex and 290–475°C for the gabbros. The ⁸⁷Sr/⁸⁶Sr isotope ratios show the widest range and highest values in the extrusive rocks (0.70316–0.70495), and generally the lowest values and the narrowest range in the sheeted dyke complex (0.70338–0.70377). The minimum water/rock ratios calculated show the largest variations in volcanic rocks and gabbros (approximately 0–14), and generally the lowest values and range in the sheeted dyke complex (approximately 1–3). The δD values of epidote (?1 to ?12‰), together with the δ¹⁸O calculated for Ordovician seawater, are similar to those of present‐day seawater. Volcanic rocks experienced both cold and warm water circulation, resulting in the observed K₂O‐enrichment and the largest scatter in the δ¹⁸O values. As a result of metal leaching in the hot reaction zone above a magma chamber, Zn is strongly depleted in the gabbros but enriched in the sheeted dyke complex because of precipitation from upwelling of discharged hydrothermal fluids. The present study demonstrates that the near intact effect of ocean floor hydrothermal activity is preserved in the upper part of the SSOC crust, despite the influence of regional lower greenschist facies metamorphism.     

Isotopically Enriched Geogenic δ81Br and δ37Cl: Primary Evidence for the Ascending Brine Model

Mass balance calculations and hydrodynamics of groundwater flow suggest that the solutes in brines of the coastal sabkha aquifer from the Emirate of Abu Dhabi are derived largely from ascending geologic brines into the sabkha from the underlying formations. Solute interpretation for the ascending brine model (ABM) was based on two independent but secondary lines of evidence (solute ratios and solute fluxes). In the current study, direct primary evidence for this ABM was provided through analyses of δ⁸¹Br, δ³⁷Cl, and ⁸⁷Sr/⁸⁶Sr. Different solute histories of geologic brine and sea water provide an “isotopic fingerprint” that can uniquely distinguish between the two possible sources. Samples from the coastal sabkha aquifer of Abu Dhabi were determined to have a mean δ⁸¹Br of 1.17‰ that is statistically equal, at the 95% confidence level, to the mean of 1.11‰ observed in the underlying geologic brine and statistically different than sea water. Similarly, the δ³⁷Cl in sabkha brine has a mean of 0.25‰ and is statistically equal to a mean of 0.21‰ in the underlying geologic brines at the 95% confidence level and statistically different from sea water. Also, dissolved strontium isotope data are consistent with the ABM and even with the complex set of processes in the sabkha, the variance in strontium isotope results is similar to the geologic brine. These observations provide primary direct evidence consistent that the major source of these solutes (and presumably others in the aquifer) is from discharging geologic brines, not from adjacent sea water.     

Isotopic composition of precipitation in a topographically steep,seasonally snow‐dominated watershed and implications of variations from the global meteoric water line

The local meteoric water line (LMWL), the functional relationship between locally measured values of δ¹⁸O and δ²H in precipitation, represents the isotopic composition of water entering hydrologic systems. The degree to which the LMWL departs from the global meteoric water line (GMWL), moreover, can reveal important information about meteoric sources of water (e.g. oceanic or terrestrial) and atmospheric conditions during transport. Here we characterize the isotopic composition of precipitation within an experimental watershed in the Western US that is subject to large topographic and seasonal gradients in precipitation. Interpreting the hydrometeorologic and spatial controls on precipitation, we constructed a seasonally weighted LMWL for southwestern Idaho that is expressed by the equation δ²H = 7.40 × δ¹⁸O ? 2.17. A seasonally weighted LMWL that is based on weighting isotopic concentrations by climatic precipitation volumes is novel, and we argue better represents the significant seasonality of precipitation in the region. The developed LMWL is considerably influenced by the semiarid climate experienced in southwest Idaho, yielding a slope and y‐intercept lower than the GMWL (δ²H = 8 × δ¹⁸O + 10). Moderate to strong correlations exist between the isotopic composition of precipitation from individual events and surface meteorologic variables, specifically surface air temperature, relative humidity, and precipitation amount. A strong negative correlation exists between the annual average isotopic composition of precipitation and elevation at individual collection sites, with a lapse rate of ?0.22‰/100 m. Copyright © 2016 John Wiley & Sons, Ltd.     

Geochemical evidence for mixing of magmatic fluids with seawater,Nisyros hydrothermal system,Greece

The chemical and isotopic compositions (δD_H2O, δ¹⁸O_H2O, δ¹⁸O_CO2, δ¹³C_CO2, δ³⁴S, and He/N₂ and He/Ar ratios) of fumarolic gases from Nisyros, Greece, indicate that both arc-type magmatic water and local seawater feed the hydrothermal system. Isotopic composition of the deep fluid is estimated to be +4.9±0.5‰ for δ¹⁸O and ?11±5‰ for δD corresponding to a magmatic water fraction of 0.7. Interpretation of the stable water isotopes was based on liquid–vapor separation conditions obtained through gas geothermometry. The H₂–Ar, H₂–N₂, and H₂–H₂O geothermometers suggest reservoir temperatures of 345±15 °C, in agreement with temperatures measured in deep geothermal wells, whereas a vapor/liquid separation temperature of 260±30 °C is indicated by gas equilibria in the H₂O–H₂–CO₂–CO–CH₄ system. The largest magmatic inputs seem to occur below the Stephanos–Polybotes Micros crater, whereas the marginal fumarolic areas of Phlegeton–Polybotes Megalos craters receive a smaller contribution of magmatic gases.     

Isotope hydrology of the Allt a' Mharcaidh catchment,Cairngorms, Scotland: implications for hydrological pathways and residence times

The hydrology of oxygen‐18 (¹⁸O) isotopes was monitored between 1995 and 1998 in the Allt a' Mharcaidh catchment in the Cairngorm Mountains, Scotland. Precipitation (mean δ¹⁸O=−7·69‰) exhibited strong seasonal variation in δ¹⁸O values over the study period, ranging from −2·47‰ in the summer to −20·93‰ in the winter months. As expected, such variation was substantially damped in stream waters, which had a mean and range of δ¹⁸O of −9·56‰ and −8·45 to −10·44‰, respectively. Despite this, oxygen‐18 proved a useful tracer and streamwater δ¹⁸O variations could be explained in terms of a two‐component mixing model, involving a seasonally variable δ¹⁸O signature in storm runoff, mixing with groundwater characterized by relatively stable δ¹⁸O levels. Variations in soil water δ¹⁸O implied the routing of depleted spring snowmelt and enriched summer rainfall into streamwaters, probably by near‐surface hydrological pathways in peaty soils. The relatively stable isotope composition of baseflows is consistent with effective mixing processes in shallow aquifers at the catchment scale. Examination of the seasonal variation in δ¹⁸O levels in various catchment waters provided a first approximation of mean residence times in the major hydrological stores. Preliminary estimates are 0·2–0·8 years for near‐surface soil water that contributes to storm runoff and 2 and >5 years for shallow and deeper groundwater, respectively. These ¹⁸O data sets provide further evidence that the influence of groundwater on the hydrology and hydrochemistry of upland catchments has been underestimated. Copyright © 2000 John Wiley & Sons, Ltd.     

Groundwater mixing between different aquifer types in a complex structural setting discerned by elemental and stable isotope geochemistry

Karst aquifers are well known for their intricate stratigraphy and geologic structures, which make groundwater characterization challenging because flowpaths and recharge sources are complex and difficult to evaluate. Geochemical data, collected from ten closely spaced production wells constructed in two karst aquifers (Bangor Limestone (Mb) and Tuscumbia Limestone/Fort Payne Chert (Mftp)) in Trussville, north‐central Alabama, illustrate two distinctive groundwater end‐members: (1) higher major ion, dissolved inorganic carbon, conductivity, alkalinity concentrations, heavier δ¹³C ratios (max: −10.2 ± 0.2‰ Vienna Pee Dee Belemnite (PDB)) and lower residence times (mean: 19.5 ± 2 years, n = 2) of groundwater in the Mb aquifer and (2) lower constituent concentrations, lighter δ¹³C ratios (min: −13.4 ± 0.2‰ PDB) and longer residence times of groundwater (mean: 23.6 ± 2 years, n = 4) in the Mftp aquifer. Summer and fall data and the binary mixing model show aquifer inter‐flow mixing along solution fractures and confirms the distinctive groundwater geochemistry of the two aquifers. Lowering of static water levels over the summer (drawdown from 2 to 5.2 m) leads to more reducing groundwater conditions (lower Eh values) and slightly enriched δ¹⁸O and δD ratios during the fall [δ¹⁸O: −4.8 ± 0.1 to −5.4 ± 0.1‰ Vienna Standard Mean Oceanic Water (VSMOW), n = 9; δD: −25.4 ± 1 to −27.4 ± 1‰ VSMOW, n = 9] when compared with summer season samples (δ¹⁸O: −5.1 ± 0.1 to −5.7 ± 0.1‰ VSMOW, n = 11; δD: −25.0 ± 1 to −30.6 ± 1‰ VSMOW, n = 11). GIS analyses confirm the localized origin of recharge to the investigated aquifers. The combination of GIS, field parameters and geochemistry analyses can be successfully used to identify recharge sources, evaluate groundwater flow and transport pathways and to improve understanding of how groundwater withdrawals impact the sustainability and susceptibility to contamination of karst aquifers. Copyright © 2015 John Wiley & Sons, Ltd.